Synergistic pesticidal compositions and related methods

ABSTRACT

A pesticidal composition comprises a synergistically effective amount of a flonicamid-based selective homopteran feeding blocker compound and a pesticide selected from N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (I), N-(3-chloro-1-(pyridine-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide (II), or any agriculturally acceptable salt thereof. A method of controlling pests comprises applying the pesticidal composition near a population of pests. A method of protecting a plant from infestation and attack by pests comprises contacting the plant with the synergistic pesticidal composition.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of the filing date of U.S.Provisional Patent Application Ser. No. 61/894,158, filed Oct. 22, 2013,for “SYNERGISTIC PESTICIDAL COMPOSITIONS AND RELATED METHODS,” pending,the disclosure of which is hereby incorporated herein in its entirety bythis reference.

TECHNICAL FIELD

This disclosure relates to the field of compounds having pesticidalutility against pests in Phyla Nematoda, Arthropoda, and/or Mollusca,processes to produce such compounds and intermediates used in suchprocesses. These compounds may be used, for example, as nematicides,acaricides, miticides, and/or molluscicides.

BACKGROUND

Controlling pest populations is essential to human health, modernagriculture, food storage, and hygiene. There are more than ten thousandspecies of pests that cause losses in agriculture and the worldwideagricultural losses amount to billions of U.S. dollars each year.Accordingly, there exists a continuous need for new pesticides and formethods of producing and using such pesticides.

The Insecticide Resistance Action Committee (IRAC) has classifiedinsecticides into categories based on the best available evidence of themode of action of such insecticides. Insecticides in the IRAC Mode ofAction Group 9C are selective homopteran feeding blockers that areflonicamid-based compounds. The insecticides in this class are believedto cause selective inhibition of feeding in the affected insects.Flonicamid is N-(cyanomethyl)-4-(trifluoromethyl)-3-pyridinecarboxamide.

Although the rotational application of pesticides having different modesof action may be adopted for good pest management practice, thisapproach does not necessarily give satisfactory insect control.Furthermore, even though combinations of pesticides have been studied, ahigh synergistic action has not always been found.

DETAILED DESCRIPTION

As used herein, the term “synergistic effect” or grammatical variationsthereof means and includes a cooperative action encountered in acombination of two or more active compounds in which the combinedactivity of the two or more active compounds exceeds the sum of theactivity of each active compound alone.

The term “synergistically effective amount,” as used herein, means andincludes an amount of two or more active compounds that provides asynergistic effect defined above.

The term “pesticidally effective amount,” as used herein, means andincludes an amount of active pesticide that causes an adverse effect tothe at least one pest, wherein the adverse effect may include deviationsfrom natural development, killing, regulation, or the like.

The term “control” or grammatical variations thereof means and includesregulating the number of living pests or regulating the number of viableeggs of the pests or both.

The term “flonicamid-based selective homopteran feeding blockercompound,” as used herein, means and includes any insecticides that areclassified by the Insecticide Resistance Action Committee (IRAC), basedon the best available evidence of the mode of action, to be within theIRAC Mode of Action Group 9C.

In one particular embodiment, a pesticidal composition comprises asynergistically effective amount of a flonicamid-based selectivehomopteran feeding blocker compound in combination with a pesticideselected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

It is appreciated that a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof may be oxidized tothe corresponding sulfone in the presence of oxygen.

As shown in the examples, the existence of synergistic effect isdetermined using the method described in Colby S. R., “CalculatingSynergistic and Antagonistic Responses of Herbicide Combinations,”Weeds, 1967, 15, 20-22.

Surprisingly, it has been found that the pesticidal composition of thepresent disclosure has superior pest control at lower levels of thecombined concentrations of the flonicamid-based selective homopteranfeeding blocker compound and the pesticide employed than that which maybe achieved when the flonicamid-based selective homopteran feedingblocker compound and the pesticide are applied alone. In other words,the synergistic pesticidal composition is not a mere admixture of twoactive compounds resulting in the aggregation of the properties of theactive compounds employed in the composition.

In some embodiments, the pesticidal compositions may comprise asynergistically effective amount of a flonicamid-based compound incombination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

In other embodiments, the pesticidal compositions may comprise asynergistically effective amount of flonicamid in combination with apesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

Table 1A shows weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the flonicamid-based selectivehomopteran feeding blocker compound in the synergistic pesticidalcompositions. In some embodiments, the weight ratio of the pesticide tothe flonicamid-based selective homopteran feeding blocker compound maybe between about 20:1 and about 1:20. In some embodiments, the weightratio of the pesticide to the flonicamid-based selective homopteranfeeding blocker compound may be between about 15:1 and about 1:15. Insome embodiments, the weight ratio of the pesticide to theflonicamid-based selective homopteran feeding blocker compound may bebetween about 10:1 and about 1:10. In some embodiments, the weight ratioof the pesticide to the flonicamid-based selective homopteran feedingblocker compound may be between about 5:1 and about 1:5. In someembodiments, the weight ratio of the pesticide to the flonicamid-basedselective homopteran feeding blocker compound may be between about 4:1and about 1:4. In some embodiments, the weight ratio of the pesticide tothe flonicamid-based selective homopteran feeding blocker compound maybe between about 3:1 and about 1:3. In some embodiments, the weightratio of the pesticide to the flonicamid-based selective homopteranfeeding blocker compound may be between about 2:1 and about 1:2. In someembodiments, the weight ratio of the pesticide to the flonicamid-basedselective homopteran feeding blocker compound may be between about 1:1.Additionally, the weight ratio limits of the pesticide to theflonicamid-based selective homopteran feeding blocker compound in theaforementioned embodiments may be interchangeable. By way ofnon-limiting example, the weight ratio of the pesticide to theflonicamid-based selective homopteran feeding blocker compound may bebetween about 1:3 and about 20:1.

TABLE 1A Range of the Weight Ratio of Pesticide I or II toFlonicamid-Based Selective No. Homopteran Feeding Blocker 1 20:1 to 1:202 15:1 to 1:15 3 10:1 to 1:10 4 5:1 to 1:5 5 4:1 to 1:4 6 3:1 to 1:3 72:1 to 1:2 8 1:1

Weight ratios of the pesticide (I), (II), or any agriculturallyacceptable salt thereof to the flonicamid-based selective homopteranfeeding blocker envisioned to be synergistic pesticidal compositions maybe depicted as X:Y; wherein X is the parts by weight of the pesticide(I), (II), or any agriculturally acceptable salt thereof, and Y is theparts by weight of the flonicamid-based selective homopteran feedingblocker. The numerical range of the parts by weight for X is 0<X≦20 andthe parts by weight for Y is 0<Y≦20 as shown graphically in table 1B. Byway of non-limiting example, the weight ratio of the pesticide to theflonicamid-based selective homopteran feeding blocker compound may beabout 20:1.

TABLE 1B Flonicamid- 20 X, Y X, Y based 15 X, Y X, Y X, Y selective 10X, Y X, Y homopteran 5 X, Y X, Y X, Y X, Y feeding 4 X, Y X, Y X, Y X, Yblocker (Y) 3 X, Y X, Y X, Y X, Y X, Y X, Y Parts by 2 X, Y X, Y X, Y X,Y weight 1 X, Y X, Y X, Y X, Y X, Y X, Y X, Y X, Y 1 2 3 4 5 10 15 20Pesticide (I or II) (X) Parts by weight

Ranges of weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the flonicamid-based selectivehomopteran feeding blocker envisioned to be synergistic pesticidalcompositions may be depicted as X₁:Y₁ to X₂:Y₂, wherein X and Y aredefined as above. In one particular embodiment, the range of weightratios may be X₁:Y₁ to X₂:Y₂, wherein X₁>Y₁ and X₂<Y₂. By way ofnon-limiting example, the range of weight ratios of the pesticide to theflonicamid-based selective homopteran feeding blocker compound may bebetween about 3:1 and about 1:3. In some embodiments, the range ofweight ratios may be X₁:Y₁ to X₂:Y₂, wherein X₁>Y₁ and X₂>Y₂. By way ofnon-limiting example, the range of weight ratios of the pesticide to theflonicamid-based selective homopteran feeding blocker compound may bebetween about 15:1 and about 3:1. In further embodiments, the range ofweight ratios may be X₁:Y₁ to X₂:Y₂, wherein X₁<Y₁ and X₂<Y₂. By way ofnon-limiting example, the range of weight ratios of the pesticide to theflonicamid-based selective homopteran feeding blocker compound may bebetween about 1:3 and about 1:20.

Table 1C shows further weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the flonicamid-based selectivehomopteran feeding blocker compound in the synergistic pesticidalcompositions, according to particular embodiments of present disclosure.In some particular embodiments, the weight ratio of the pesticide to theflonicamid-based selective homopteran feeding blocker compound may be nomore than about 64:1. In yet further embodiments, the weight ratio ofthe pesticide to the flonicamid-based selective homopteran feedingblocker compound may be no more than about 16:1.

TABLE 1C Dose Rate of Weight Ratio of Dose Rate Flonicamid-BasedPesticide (I or II) Of Pesticide Selective Homopteran toFlonicamid-Based (I or II) Feeding Blocker Selective Homopteran (weight%) Compound (weight %) Feeding Blocker Compound 0.0025 0.000039 ≦64:10.0025 0.000156 ≦16:1 0.000625 0.000039 ≦16:1

The weight ratio of the pesticide to the flonicamid-based selectivehomopteran feeding blocker compound in the synergistic pesticidalcomposition may be varied and different from those described in table1A, table 1B, and table 1C. One skilled in the art recognizes that thesynergistic effective amount of the combination of active compounds mayvary accordingly to various prevailing conditions. Non-limiting examplesof such prevailing conditions may include the type of pests, the type ofcrops, the mode of application, the application timing, the weatherconditions, the soil conditions, the topographical character, or thelike. It is understood that one skilled in the art may readily determinethe synergistic effective amount of the flonicamid-based selectivehomopteran feeding blocker compound and the pesticide accordingly to theprevailing conditions.

In some embodiments, the pesticidal composition may comprise asynergistically effective amount of a flonicamid-based selectivehomopteran feeding blocker compound in combination with a pesticideselected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof, and aphytologically-acceptable inert carrier (e.g., solid carrier, or liquidcarrier).

In further embodiments, the pesticidal composition may further compriseat least one additive selected from a surfactant, a stabilizer, anemetic agent, a disintegrating agent, an antifoaming agent, a wettingagent, a dispersing agent, a binding agent, dye, filler, or combinationsthereof.

In particular embodiments, each of the active compounds (aflonicamid-based selective homopteran feeding blocker compound and apesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof) may be formulatedseparately as a wettable powder, emulsifiable concentrate, aqueous orliquid flowable, suspension concentrate or any one of the conventionalformulations used for pesticides, and then tank-mixed in the field withwater or other liquid for application as a liquid spray mixture. Whendesired, the separately formulated pesticides may also be appliedsequentially.

In some embodiments, the synergistic pesticidal composition may beformulated into a more concentrated primary composition, which is thendiluted with water or other diluent before use. In such embodiments, thesynergistic pesticidal composition may further comprise a surface activeagent.

In one particular embodiment, the method of protecting a plant frominfestation and attack by insects comprises contacting the plant with apesticidal composition comprising a synergistically effective amount ofa flonicamid-based selective homopteran feeding blocker compound incombination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

In some embodiments, the pesticidal compositions may be in the form ofsolid. Non-limiting examples of the solid forms may include powder, dustor granular formulations.

In other embodiments, the pesticidal compositions may be in the form ofliquid formulation. Examples of the liquid forms may include, but arenot limited to, dispersion, suspension, emulsion or solution inappropriate liquid carrier. In particular embodiments, the synergisticpesticidal compositions may be in the form of liquid dispersion, whereinthe synergistic pesticidal compositions may be dispersed in water orother agriculturally suitable liquid carrier.

In certain embodiments, the synergistic pesticidal compositions may bein the form of solution in an appropriate organic solvent. In oneembodiment, the spray oils, which are widely used in agriculturalchemistry, may be used as the organic solvent for the synergisticpesticidal compositions.

In one particular embodiment, the method of controlling pests comprisesapplying a pesticidal composition near a population of pests, whereinthe pesticidal composition comprises a synergistically effective amountof a flonicamid-based selective homopteran feeding blocker compound incombination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

In some embodiments, the method of controlling pests comprises applyinga pesticidal composition near a population of pests, wherein thepesticidal composition comprises a synergistically effective amount offlonicamid in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

The control of pests may be achieved by applying a pesticidallyeffective amount of the synergistic pesticidal compositions in form ofsprays, topical treatment, gels, seed coatings, microcapsulations,systemic uptake, baits, eartags, boluses, foggers, fumigants aerosols,dusts, or the like.

These disclosed pesticidal compositions may be used, for example, asnematicides, acaricides, miticides, and/or molluscicides.

The pesticidal composition of the present disclosure may be used tocontrol a wide variety of insects. As a non-limiting example, in one ormore embodiments, the pesticidal composition may be used to control oneor more members of at least one of Phylum Arthropoda, Phylum Nematoda,Subphylum Chelicerata, Subphylum Myriapoda, Subphylum Hexapoda, ClassInsecta, Class Arachnida, and Class Symphyla. In at least someembodiments, the method of the present disclosure may be used to controlone or more members of at least one of Class Insecta and ClassArachnida.

As a non-limiting example, in one or more embodiments, the method of thepresent disclosure may be used to control one or more members of atleast one of Phylum Arthropoda, Phylum Nematoda, Subphylum Chelicerata,Subphylum Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida,and Class Symphyla. In at least some embodiments, the method of thepresent disclosure may be used to control one or more members of atleast one of Class Insecta and Class Arachnida.

In additional embodiments, the method of the present disclosure may beused to control members of the Order Coleoptera (beetles) including, butnot limited to, Acanthoscelides spp. (weevils), Acanthoscelides obtectus(common bean weevil), Agrilus planipennis (emerald ash borer), Agriotesspp. (wireworms), Anoplophora glabripennis (Asian longhorned beetle),Anthonomus spp. (weevils), Anthonomus grandis (boll weevil), Aphidiusspp., Apion spp. (weevils), Apogonia spp. (grubs), Ataenius spretulus(Black Turfgrass Ataenius), Atomaria linearis (pygmy mangold beetle),Aulacophore spp., Bothynoderes punctiventris (beet root weevil), Bruchusspp. (weevils), Bruchus pisorum (pea weevil), Cacoesia spp.,Callosobruchus maculatus (southern cow pea weevil), Carpophilushemipteras (dried fruit beetle), Cassida vittata, Cerosterna spp.,Cerotoma spp. (chrysomelids), Cerotoma trifurcata (bean leaf beetle),Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis (cabbage seedpodweevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp.(chrysomelids), Colaspis spp. (soil beetles), Conoderus scalaris,Conoderus stigmosus, Conotrachelus nenuphar (plum curculio), Cotinusnitidis (Green June beetle), Crioceris asparagi (asparagus beetle),Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes pusillus(flat grain beetle), Cryptolestes turcicus (Turkish grain beetle),Ctenicera spp. (wireworms), Curculio spp. (weevils), Cyclocephala spp.(grubs), Cylindrocpturus adspersus (sunflower stem weevil), Deporausmarginatus (mango leaf-cutting weevil), Dermestes lardarius (larderbeetle), Dermestes maculates (hide beetle), Diabrotica spp.(chrysomelids), Epilachna varivestis (Mexican bean beetle), Faustinuscubae, Hylobius pales (pales weevil), Hypera spp. (weevils), Hyperapostica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil),Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers),Lasioderma serricorne (cigarette beetle), Leptinotarsa decemlineata(Colorado potato beetle), Liogenys fuscus, Liogenys suturalis,Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (woodbeetles/powder post beetles), Maecolaspis joliveti, Megascelis spp.,Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle),Melolontha melolontha (common European cockchafer), Oberea brevis,Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilusmercator (merchant grain beetle), Oryzaephilus suninamensis (sawtoothedgrain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cerealleaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp.(May/June beetle), Phyllophaga cuyabana (chrysomelids), Phynchites spp.,Popillia japonica (Japanese beetle), Prostephanus truncates (largergrain borer), Rhizopertha dominica (lesser grain borer), Rhizotrogusspp. (European chafer), Rhynchophorus spp. (weevils), Scolytus spp.(wood beetles), Shenophorus spp. (Billbug), Sitona lineatus (pea leafweevil), Sitophilus spp. (grain weevils), Sitophilus granaries (granaryweevil), Sitophilus oryzae (rice weevil), Stegobium paniceum (drugstorebeetle), Tribolium spp. (flour beetles), Tribolium castaneum (red flourbeetle), Tribolium confusum (confused flour beetle), Trogodermavariabile (warehouse beetle), and Zabrus tenebioides.

In other embodiments, the method of the present disclosure may also beused to control members of the Order Dermaptera (earwigs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Dictyoptera (cockroaches)including, but is not limited to, Blattella germanica (Germancockroach), Blatta orientalis (oriental cockroach), Parcoblattapennylvanica, Periplaneta americana (American cockroach), Periplanetaaustraloasiae (Australian cockroach), Periplaneta brunnea (browncockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselussuninamensis (Surinam cockroach), and Supella longipalpa (brownbandedcockroach).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Diptera (true flies) including, but isnot limited to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfablotch leafminer), Agromyza spp. (leaf miner flies), Anastrepha spp.(fruit flies), Anastrepha suspensa (Caribbean fruit fly), Anopheles spp.(mosquitoes), Bactrocera spp. (fruit flies), Bactrocera cucurbitae(melon fly), Bactrocera dorsalis (oriental fruit fly), Ceratitis spp.(fruit flies), Ceratitis capitata (Mediterranean fruit fly), Chrysopsspp. (deer flies), Cochliomyia spp. (screwworms), Contarinia spp. (Gallmidges), Culex spp. (mosquitoes), Dasineura spp. (gall midges),Dasineura brassicae (cabbage gall midge), Delia spp., Delia platura(seedcorn maggot), Drosophila spp. (vinegar flies), Fannia spp. (filthflies), Fannia canicularis (little house fly), Fannia scalaris (latrinefly), Gasterophilus intestinalis (horse bot fly), Gracillia perseae,Haematobia irritans (horn fly), Hylemyia spp. (root maggots), Hypodermalineatum (common cattle grub), Liriomyza spp. (leafminer flies),Liriomyza brassica (serpentine leafminer), Liriomyza sativae (vegetableleafminer), Melophagus ovinus (sheep ked), Musca spp. (muscid flies),Musca autumnalis (face fly), Musca domestica (house fly), Oestrus ovis(sheep bot fly), Oscinella frit (frit fly), Pegomyia betae (beetleafminer), Phorbia spp., Psila rosae (carrot rust fly), Rhagoletiscerasi (cherry fruit fly), Rhagoletis pomonella (apple maggot),Sitodiplosis mosellana (orange wheat blossom midge), Stomoxys calcitrans(stable fly), Tabanus spp. (horse flies), and Tipula spp. (crane flies).

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hemiptera Sub-order Heteroptera (truebugs) including, but is not limited to, Acrosternum hilare (green stinkbug), Blissus leucopterus (chinch bug), Bragada hilaris, Calocorisnorvegicus (potato mirid), Cimex hemipterus (tropical bed bug), Cimexlectularius (bed bug), Dagbertus fasciatus, Dichelops furcatus,Dysdercus suturellus (cotton stainer), Edessa meditabunda, Eurygastermaura (cereal bug), Euschistus heros, Euschistus servus (brown stinkbug), Helopeltis antonii, Helopeltis theivora (tea blight plantbug),Lagynotomus spp. (stink bugs), Leptocorisa oratorius, Leptocorisavaricornis, Lygus spp. (plant bugs), Lygus hesperus (western tarnishedplant bug), Lygus lineolaris (tarnished plant bug), Maconellicoccushirsutus, Neurocolpus longirostris, Nezara viridula (southern greenstink bug), Phytocoris spp. (plant bugs), Phytocoris califormicus,Phytocoris relativus, Piezodorus guildinii (redbanded stink bug),Poecilocapsus lineatus (fourlined plant bug), Psallus vaccinicola,Pseudacysta perseae, Scaptocoris castanea, and Triatoma spp.(bloodsucking conenose bugs/kissing bugs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Hemiptera, Sub-ordersAuchenorrhyncha (Free-living Hemipterans) and Sternorrhyncha(Plant-parasitic Hemipterans) (aphids, scales, whiteflies, leaflhoppers)including, but is not limited to, Acrythosiphon pisum (pea aphid),Adelges spp. (adelgids), Aleurodes proletella (cabbage whitefly),Aleurodicus disperses, Aleurothrixus floccosus (woolly whitefly),Aluacaspis spp., Amrasca bigutella bigutella, Aphrophora spp.(leafhoppers), Aonidiella aurantii (California red scale), Aphis spp.(aphids), Aphis gossypii (cotton aphid), Aphis pomi (apple aphid),Aulacorthum solani (foxglove aphid), Bemisia spp. (whiteflies), Bemisiaargentifolii, Bemisia tabaci (sweetpotato whitefly), Brachycolus noxius(Russian aphid), Brachycorynella asparagi (asparagus aphid), Brevenniarehi, Brevicoryne brassicae (cabbage aphid), Ceroplastes spp. (scales),Ceroplastes rubens (red wax scale), Chionaspis spp. (scales),Chrysomphalus spp. (scales), Chrysomphalus aonidum (Florida red scale)Coccus spp. (scales), Coccus pseudomagnoliarum (citricola scale),Dysaphis plantaginea (rosy apple aphid), Empoasca spp. (leafhoppers),Eriosoma lanigerum (woolly apple aphid), Icerya purchasi (cottonycushion scale), Idioscopus nitidulus (mango leafhopper), Laodelphaxstriatellus (smaller brown planthopper), Lepidosaphes spp., Macrosiphumspp., Macrosiphum euphorbiae (potato aphid), Macrosiphum granarium(English grain aphid), Macrosiphum rosae (rose aphid), Macrostelesquadrilineatus (aster leafhopper), Mahanarva frimbiolata, Metopolophiumdirhodum (rose grain aphid), Mictis longicornis, Myzus spp., Myzuspersicae (green peach aphid), Nephotettix spp. (leafhoppers),Nephotettix cinctipes (green leafhopper), Nilaparvata lugens (brownplanthopper), Paratrioza cockerelli (tomato psyllid), Parlatoriapergandii (chaff scale), Parlatoria ziziphi (ebony scale), Peregrinusmaidis (corn delphacid), Philaenus spp. (spittlebugs), Phylloxeravitifoliae (grape phylloxera), Physokermes piceae (spruce bud scale),Planococcus spp. (mealybugs), Planococcus citri (citrus mealybug),Planococcus ficus (grape mealybug), Pseudococcus spp. (mealybugs),Pseudococcus brevipes (pine apple mealybug), Quadraspidiotus perniciosus(San Jose scale), Rhopalosiphum spp. (aphids), Rhopalosiphum maidis(corn leaf aphid), Rhopalosiphum padi (oat bird-cherry aphid), Saissetiaspp. (scales), Saissetia oleae (black scale), Schizaphis graminum(greenbug), Sitobion avenae (English grain aphid), Sogatella furcifera(white-backed planthopper), Therioaphis spp. (aphids), Toumeyella spp.(scales), Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies),Trialeurodes vaporariorum (greenhouse whitefly), Trialeurodesabutiloneus (bandedwing whitefly), Unaspis spp. (scales), Unaspisyanonensis (arrowhead scale), and Zulia entreriana. In at least someembodiments, the method of the present disclosure may be used to controlMyzus persicae.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hymenoptera (ants, wasps, and sawflies)including, but not limited to, Acromyrrmex spp., Athalia rosae, Attaspp. (leafcutting ants), Camponotus spp. (carpenter ants), Diprion spp.(sawflies), Formica spp. (ants), Iridomyrmex humilis (Argentine ant),Monomorium spp., Monomorium minumum (little black ant), Monomoriumpharaonis (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex spp.(harvester ants), Polistes spp. (paper wasps), Solenopsis spp. (fireants), Tapoinoma sessile (odorous house ant), Tetranomorium spp.(pavement ants), Vespula spp. (yellow jackets), and Xylocopa spp.(carpenter bees).

In certain embodiments, the method of the present disclosure may be usedto control members of the Order Isoptera (termites) including, but notlimited to, Coptotermes spp., Coptotermes curvignathus, Coptotermesfrenchii, Coptotermes formosanus (Formosan subterranean termite),Cornitermes spp. (nasute termites), Cryptotermes spp. (drywoodtermites), Heterotermes spp. (desert subterranean termites),Heterotermes aureus, Kalotermes spp. (drywood termites), Incistitermesspp. (drywood termites), Macrotermes spp. (fungus growing termites),Marginitermes spp. (drywood termites), Microcerotermes spp. (harvestertermites), Microtermes obesi, Procornitermes spp., Reticulitermes spp.(subterranean termites), Reticulitermes banyulensis, Reticulitermesgrassei, Reticulitermes flavipes (eastern subterranean termite),Reticulitermes hageni, Reticulitermes hesperus (western subterraneantermite), Reticulitermes santonensis, Reticulitermes speratus,Reticulitermes tibialis, Reticulitermes virginicus, Schedorhinotermesspp., and Zootermopsis spp. (rotten-wood termites).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Lepidoptera (moths and butterflies)including, but not limited to, Achoea janata, Adoxophyes spp.,Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (blackcutworm), Alabama argillacea (cotton leafworm), Amorbia cuneana,Amyelosis transitella (navel orangeworm), Anacamptodes defectaria,Anarsia lineatella (peach twig borer), Anomis sabulifera (jute looper),Anticarsia gemmatalis (velvetbean caterpillar), Archips argyrospila(fruittree leafroller), Archips rosana (rose leaf roller), Argyrotaeniaspp. (tortricid moths), Argyrotaenia citrana (orange tortrix),Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaf folder),Bucculatrix thurberiella (cotton leafperforator), Caloptilia spp. (leafminers), Capua reticulana, Carposina niponensis (peach fruit moth),Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneurarosaceana (obliquebanded leafroller), Chrysodeixis spp., Cnaphalocerusmedinalis (grass leafroller), Colias spp., Conpomorpha cramerella,Cossus cossus (carpenter moth), Crambus spp. (Sod webworms),Cydiafunebrana (plum fruit moth), Cydia molesta (oriental fruit moth),Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darnadiducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers),Diatraea saccharalis (sugarcane borer), Diatraea graniosella(southwester corn borer), Earias spp. (bollworms), Earias insulata(Egyptian bollworm), Earias vitella (rough northern bollworm),Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalkborer), Epiphysias postruttana (light brown apple moth), Ephestia spp.(flour moths), Ephestia cautella (almond moth), Ephestia elutella(tobbaco moth), Ephestia kuehniella (Mediterranean flour moth), Epimecesspp., Epinotia aporema, Erionota thrax (banana skipper), Eupoeciliaambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltiaspp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (orientalfruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp.(noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea(bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothisvirescens (tobacco budworm), Hellula undalis (cabbage webworm),Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm),Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella,Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp.(noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantriadispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasenacorbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars),Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean podborer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm),Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis(rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis(European corn borer), Oxydia vesulia, Pandemis cerasana (common curranttortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus,Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms),Peridroma saucia (variegated cutworm), Perileucoptera coffeella (whitecoffee leafminer), Phthorimaea operculella (potato tuber moth),Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris rapae(imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indianmeal moth), Plutella xylostella (diamondback moth), Polychrosis viteana(grape berry moth), Prays endocarps, Prays oleae (olive moth),Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm),Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophagaincertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stemborer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella(Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.(armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda(fall armyworm), Spodoptera oridania (southern armyworm), Synanthedonspp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineolabisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper),Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), andZeuzera pyrina (leopard moth). In at least some embodiments, the methodof the present disclosure may be used to control Spodoptera exigua.

The method of the present disclosure may be used to also control membersof the Order Mallophaga (chewing lice) including, but not limited to,Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken bodylouse), and Menopon gallinea (common hen louse).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Orthoptera (grasshoppers, locusts,and crickets) including, but not limited to, Anabrus simplex (Mormoncricket), Gryllotalpidae (mole crickets), Locusta migratoria, Melanoplusspp. (grasshoppers), Microcentrum retinerve (angularwinged katydid),Pterophylla spp. (kaydids), chistocerca gregaria, Scudderia furcata(forktailed bush katydid), and Valanga nigricorni.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Phthiraptera (sucking lice) including,but not limited to, Haematopinus spp. (cattle and hog lice), Linognathusovillus (sheep louse), Pediculus humanus capitis (human body louse),Pediculus humanus humanus (human body lice), and Pthirus pubis (crablouse).

In particular embodiments, the method of the present disclosure may beused to control members of the Order Siphonaptera (fleas) including, butnot limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis(cat flea), and Pulex irritans (human flea).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Thysanoptera (thrips) including,but not limited to, Caliothrips fasciatus (bean thrips), Caliothripsphaseoli, Frankliniella fusca (tobacco thrips), Frankliniellaoccidentalis (western flower thrips), Frankliniella shultzei,Frankliniella williamsi (corn thrips), Heliothfips haemorrhaidalis(greenhouse thrips), Riphiphorothrips cruentatus, Scirtothrips spp.,Scirtothrips citri (citrus thrips), Scirtothrips dorsalis (yellow teathrips), Taeniothrips rhopalantennalis, Thrips spp., Thrips tabaci(onion thrips), and Thrips hawaiiensis (Hawaiian flower thrips).

The method of the present disclosure may be used to also control membersof the Order Thysanura (bristletails) including, but not limited to,Lepisma spp. (silverfish) and Thermobia spp. (firebrats).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Acari (mites and ticks) including, butnot limited to, Acarapsis woodi (tracheal mite of honeybees), Acarusspp. (food mites), Acarus siro (grain mite), Aceria mangiferae (mangobud mite), Aculops spp., Aculops lycopersici (tomato russet mite),Aculops pelekasi, Aculus pelekassi, Aculus schlechtendali (apple rustmite), Amblyomma americanum (lone star tick), Boophilus spp. (ticks),Brevipalpus obovatus (privet mite), Brevipalpus phoenicis (red and blackflat mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks),Dermacentor variabilis (american dog tick), Dermatophagoidespteronyssinus (house dust mite), Eotetranycus spp., Eotetranychuscarpini (yellow spider mite), Epitimerus spp., Eriophyes spp., Ixodesspp. (ticks), Metatetranycus spp., Notoedres cati, Oligonychus spp.,Oligonychus coffee, Oligonychus ilicus (southern red mite), Panonychusspp., Panonychus citri (citrus red mite), Panonychus ulmi (European redmite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemunlatus (broad mite), Rhipicephalus sanguineus (brown dog tick),Rhizoglyphus spp. (bulb mites), Sarcoptes scabiei (itch mite),Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae(twospotted spider mite), and Varroa destructor (honey bee mite).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Nematoda (nematodes) including, butnot limited to, Aphelenchoides spp. (foliar nematodes), Belonolaimusspp. (sting nematodes), Criconemella spp. (ring nematodes), Dirofilariaimmitis (dog heartworm), Ditylenchus spp. (stem and bulb nematodes),Heterodera spp. (cyst nematodes), Heterodera zeae (corn cyst nematode),Hirschmanniella spp. (root nematodes), Hoplolaimus spp. (lancenematodes), Meloidogyne spp. (root knot nematodes), Meloidogyneincognita (root knot nematode), Onchocerca volvulus (hook-tail worm),Pratylenchus spp. (lesion nematodes), Radopholus spp. (burrowingnematodes), and Rotylenchus reniformis (kidney-shaped nematode).

In at least some embodiments, the method of the present disclosure maybe used to control at least one insect in one or more of the OrdersLepidoptera, Coleoptera, Hemiptera, Thysanoptera, Isoptera, Orthoptera,Diptera, Hymenoptera, and Siphonaptera, and at least one mite in theOrder Acari.

In some embodiments, the method of controlling an insect may compriseapplying a pesticidal composition near a population of insects, whereinthe pesticidal composition comprises a synergistically effective amountof a flonicamid-based selective homopteran feeding blocker compound incombination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) or any agriculturally acceptable salt thereof, and wherein thepests comprise sap feeding insects, chewing insects, or both.

In other embodiments, the method of controlling an insect may compriseapplying a pesticidal composition near a population of pests, whereinthe pesticidal composition comprises a synergistically effective amountof flonicamid and a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) or any agriculturally acceptable salt thereof, wherein the pestscomprise sap feeding insects, chewing insects, or both.

In further embodiments, the method of controlling an insect may compriseapplying a pesticidal composition near a population of pests, whereinthe pesticidal composition comprises a synergistically effective amountof a flonicamid-based selective homopteran feeding blocker compound anda pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) or any agriculturally acceptable salt thereof, wherein the pestscomprise diamondback moth, Plutella xylostella.

In one embodiment of present disclosure, the pesticidal composition maybe used in conjunction (such as, in a compositional mixture, or asimultaneous or sequential application) with one or more compoundshaving acaricidal, algicidal, avicidal, bactericidal, fungicidal,herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal,and/or virucidal properties.

In one embodiment of present disclosure, the pesticidal composition maybe used in conjunction (such as, in a compositional mixture, or asimultaneous or sequential application) with one or more compounds thatare antifeedants, bird repellents, chemosterilants, herbicide safeners,insect attractants, insect repellents, mammal repellents, matingdisrupters, plant activators, plant growth regulators, and/orsynergists.

The pesticidal compositions of present disclosure show a synergisticeffect, providing superior pest control at lower pesticidally effectiveamounts of the combined active compounds than when a flonicamid-basedselective homopteran feeding blocker compound or a pesticide selectedfromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof is used alone.

The pesticidal compositions of present disclosure may have highsynergistic pest control and allow for a lower effective dosage rate, anincreased environmental safety, and a reduced incidence of pestresistance.

The following examples serve to explain embodiments of the presentinvention in more detail. These examples should not be construed asbeing exhaustive or exclusive as to the scope of this disclosure.

EXAMPLES Example 1 Preparation of3-((3,3,3-trifluoropropyl)thio)propanoyl chloride

A dry five-liter round bottom flask equipped with magnetic stirrer,nitrogen inlet, reflux condenser, and thermometer, was charged with3-((3,3,3-trifluoropropyl)thio)propanoic acid (prepared as described inthe PCT Publication No. WO 2013/062981 to Niyaz et al.) (188 g, 883mmol) in dichloromethane (CH₂Cl₂) (3 L). Thionyl chloride (525 g, 321mL, 4.42 mol) was added dropwise over 50 minutes. The reaction mixturewas heated to reflux (about 36° C.) for two hours, then cooled to roomtemperature (about 22° C.). The resulting mixture was concentrated undervacuum on a rotary evaporator, followed by distillation (40 Torr,product collected at a temperature of from about 123° C. to about 127°C.) to provide the title compound as a clear colorless liquid (177.3 g,86%): ¹H NMR (400 MHz, CDCl₃) δ 3.20 (t, J=7.1 Hz, 2H), 2.86 (t, J=7.1Hz, 2H), 2.78-2.67 (m, 2H), 2.48-2.31 (m, 2H); ¹⁹F NMR (376 MHz, CDCl₃)δ −66.42, −66.43, −66.44, −66.44.

Example 2 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I)

To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine(prepared as described in the U.S. Publication No. 2012/0110702 to Yapet al.) (10 g, 44.9 mmol) in CH₂Cl₂ (100 mL) at a temperature of about0° C. and under N₂ was added pyridine (5.45 mL, 67.4 mmol),4-dimethylaminopyridine (DMAP) (2.74 g, 22.45 mmol), and3-((3,3,3-trifluoropropyl)thio)propanoyl chloride (9.91 g, 44.9 mmol),sequentially. The reaction was warmed to room temperature and stirredfor one hour. The reaction mixture was poured into water (100 mL), andthe resulting mixture was stirred for five minutes. The mixture wastransferred to a separatory funnel, and the layers were separated. Theaqueous phase was extracted with CH₂Cl₂ (3×50 mL), and the combinedorganic extracts were dried over sodium sulfate (Na₂SO₄), filtered, andconcentrated in vacuo. The crude product was purified via normal phaseflash chromatography (0% to 100% EtOAc/CH₂Cl₂) to provide the desiredproduct as a pale yellow solid (17.21 g, 89%): IR (thin film) 1659 cm⁻¹;¹H NMR (400 MHz, CDCl₃) δ 8.95 (d, J=2.6 Hz, 1H), 8.63 (dd, J=4.7, 1.3Hz, 1H), 8.05 (ddd, J=8.3, 2.7, 1.4 Hz, 1H), 7.96 (s, 1H), 7.47 (dd,J=8.3, 4.8 Hz, 1H), 3.72 (q, J=7.1 Hz, 2H), 2.84 (t, J=7.2 Hz, 2H), 2.66(m, 2H), 237 (t, J=7.2 Hz, 2H), 2.44 (m, 2H), 1.17 (t, J=7.2 Hz, 3H);ESIMS m/z 409 ([M+2H]⁺).

Example 3 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II)

To a solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) (500 mg, 1.229 mmol) in hexafluoroisopropanol (5 mL) stirring atroom temperature was added 30% hydrogen peroxide (523 mg, 4.92 mmol).The solution was stirred at room temperature for 15 minutes. It wasquenched with saturated sodium sulfite solution and extracted withCH₂Cl₂. Silica gel chromatography (0%-10% MeOH/CH₂Cl₂) gave the titlecompound as white semi-solid (495 mg, 95%): IR (thin film) 1660 cm⁻¹; ¹HNMR (400 MHz, CDCl₃) δ 8.96 (d, J=2.4 Hz, 1H), 8.64 (dd, J=4.7, 1.4 Hz,1H), 8.07-8.00 (m, 2H), 7.46 (ddd, J=8.3, 4.8, 0.7 Hz, 1H), 3.85-3.61(m, 2H), 3.23-3.08 (m, 1H), 3.03-2.76 (m, 3H), 2.74-2.52 (m, 4H), 1.18(t, J=7.2 Hz, 3H); ESIMS m/z 423 ([M+H]⁺).

Example 4 Determination of the Existence of Synergic Effect

The method described in Colby S. R., “Calculating Synergistic andAntagonistic Responses of Herbicide Combinations,” Weeds, 1967, 15,20-22 was used to determine an existence of synergic effect between theflonicamid-based selective homopteran feeding blocker compound and thepesticide in the formulated pesticidal composition. In this method, thepercent insect control of the formulated pesticidal composition asobserved in the study was compared to the “expected” percent control (E)as calculated by equation (1) (hereinafter “Colby's equation”) below:

$\begin{matrix}{E = {X + Y - \left( \frac{XY}{100} \right)}} & (1)\end{matrix}$

where

X is the percentage of control with the first pesticide at a given rate(p),

Y is the percentage of control with the second pesticide at a given rate(q), and

E is the expected control by the first and second pesticide at a rate ofp+q.

If the observed percent control of the formulated pesticidal is greaterthan E, there is a synergistic effect between the flonicamid-basedselective homopteran feeding blocker compound and the pesticide in theformulated pesticidal composition. If the observed percent control ofthe formulated pesticidal is equaled to or less than E, there is nosynergistic effect between the flonicamid-based selective homopteranfeeding blocker compound and the pesticide in the formulated pesticidalcomposition.

Example 5 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and Flonicamid Against Diamondback Moth, Plutella xylostella Example5A

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-trifluoropropyl)thio)propanamide(hereinafter “compound I”) with about 0.000156 weight % of flonicamid.

The bioassays were performed for different active compounds. Cabbageplants with about two to three new-growth-true leaf stage were treatedwith different active compounds using a track sprayer application at 400L/Ha spray volume. Three second-instar diamondback moth, Plutellaxylostella, were infested onto each leaf disc. The percent controldetermined three days after the treatment were as shown in table 2. Thepercent control of the pesticidal composition against diamondback moth,Plutella xylostella, was determined as the “Observed” action, andcompared to those obtained by using about 0.0025 weight % of compound I,and using about 0.000156 weight % of flonicamid alone. The “Colby'sExpected Action” was calculated using Colby's equation as discussedpreviously.

TABLE 2 % Control Treatment for Dose Rate Three Days Diamondback Moth(weight %) After Treatment Compound I 0.0025   0% Flonicamid  0.0001564.17% Compound I (+) Flonicamid 0.0025 + 0.000156 12.5% Observed ActionCompound I (+)Flonicamid 0.0025 + 0.000156  4.2% Colby's Expected ActionCompound I (+) Flonicamid 0.0025 + 0.000156  8.3% Differences: Observedvs. Expected

As shown in table 2, the pesticidal compound I showed no control againstdiamondback moth after three days of the treatment. Furthermore, theobserved percent control of the pesticidal composition againstdiamondback moth (12.5%) three days after the treatments was higher thanthe expected percentage control according to Colby's equation (4.2%).This was almost 200% improvement over the Colby's expected action.Therefore, the pesticidal composition comprising 0.0025 weight % ofcompound I and about 0.000156 weight % of flonicamid showed significantsynergistic effect against diamondback moth.

Example 5B

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound I with about 0.000039 weight % of flonicamid.

The bioassays were performed wherein different active compounds weretested against diamondback moth, Plutella xylostella, using theprocedure described in example 5A. The percent control againstdiamondback moth determined three days after the treatment were as shownin table 3.

TABLE 3 % Control Treatment for Dose Rate Three Days Diamondback Moth(weight %) After Treatment Compound I 0.0025   0% Flonicamid  0.0000394.17% Compound I (+) Flonicamid 0.0025 + 0.000039 16.67%  ObservedAction Compound I (+)Flonicamid 0.0025 + 0.000039 4.20% Colby's ExpectedAction Compound I (+) Flonicamid 0.0025 + 0.000039 12.47%  Differences:Observed vs. Expected

As shown in table 3, similar to example 5A, the pesticidal compound Ishowed no control against diamondback moth after three days of thetreatment. The observed percent control of the pesticidal compositionagainst diamondback moth (16.67%) three days after the treatments washigher than the expected percentage control according to Colby'sequation (4.20%). This was almost 300% improvement over the Colby'sexpected action. Therefore, the pesticidal composition comprising 0.0025weight % of compound I and about 0.000039 weight % of flonicamid showedsignificant synergistic effect against diamondback moth.

Example 5C

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound I with about 0.000039 weight % offlonicamid.

The bioassays were performed wherein different active compounds weretested against diamondback moth, Plutella xylostella, using theprocedure described in example 5A. The percent control againstdiamondback moth determined three days after the treatment were as shownin table 4.

TABLE 4 % Control Treatment for Dose Rate Three Days Diamondback Moth(weight %) After Treatment Compound I 0.000625   0% Flonicamid 0.0000394.17% Compound I (+) Flonicamid 0.000625 + 0.000039 12.5% ObservedAction Compound I (+)Flonicamid 0.000625 + 0.000039 4.20% Colby'sExpected Action Compound I (+) Flonicamid 0.000625 + 0.000039  8.3%Differences: Observed vs. Expected

As shown in table 4, similar to example 5A, the pesticidal compound Ishowed no control against diamondback moth after three days of thetreatment. The observed percent control of the pesticidal compositionagainst diamondback moth (12.5%) three days after the treatments washigher than the expected percentage control according to Colby'sequation (4.20%). This was almost 200% improvement over the Colby'sexpected action. Therefore, the pesticidal composition comprising0.000625 weight % of compound I and about 0.000039 weight % offlonicamid showed significant synergistic effect against diamondbackmoth.

Example 6 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) orN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and Flonicamid

A pesticidal composition may be prepared by thoroughly mixing compound I(weight %) or compound II (weight %) with flonicamid (weight %).

The bioassays may be performed for different active compounds againstDiamondback Moth, Plutella xylostella, using the same procedure as thatdescribed in example 5. The percent control may be determined some timeafter the treatment.

The observed percent control of the pesticidal composition againstdiamondback moth is expected to be higher than the expected percentagecontrol according to Colby's equation. Therefore, the pesticidalcomposition comprising compound I (weight %) or compound II (weight %)and flonicamid (weight %) is expected to show synergistic effect againstdiamondback moth.

While the present disclosure may be susceptible to various modificationsand alternative forms, specific embodiments have been described by wayof example in detail herein. However, it should be understood that thepresent disclosure is not intended to be limited to the particular formsdisclosed. Rather, the present disclosure is to cover all modifications,equivalents, and alternatives falling within the scope of the presentdisclosure as defined by the following appended claims and their legalequivalents.

We claim:
 1. A pesticidal composition comprising a synergisticallyeffective amount of: a flonicamid-based selective homopteran feedingblocker compound; and a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.


2. The composition of claim 1, wherein the flonicamid-based selectivehomopteran feeding blocker compound comprises flonicamid.
 3. Thecomposition of claim 1, further comprising a phytologically-acceptableinert carrier.
 4. The composition of claim 1, further comprising anadditive selected from a surfactant, a stabilizer, an emetic agent, adisintegrating agent, an antifoaming agent, a wetting agent, adispersing agent, a binding agent, dye, filler, or combinations thereof.5. The composition of claim 1, further comprising one or more compoundshaving acaricidal, algicidal, avicidal, bactericidal, fungicidal,herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal,virucidal or combinations thereof properties.
 6. The composition ofclaim 1, further comprising one or more compounds that are antifeedants,bird repellents, chemosterilants, herbicide safeners, insectattractants, insect repellents, mammal repellents, mating disrupters,plant activators, plant growth regulators, synergists, or combinationsthereof.
 7. The composition of claim 1, wherein a weight ratio of thepesticide selected from (I), (II) or any agriculturally acceptable saltthereof to the flonicamid-based selective homopteran feeding blockercompound is no more than about 64:1.
 8. The composition of claim 1,wherein a weight ratio of the pesticide selected from (I), (II) or anyagriculturally acceptable salt thereof to the flonicamid-based selectivehomopteran feeding blocker compound is no more than about 16:1
 9. Thecomposition of claim 1, wherein the weight ratio of the pesticide (I),(II), or any agriculturally acceptable salt thereof and theflonicamid-based selective homopteran feeding blocker is X:Y; wherein, Xis the parts by weight of the pesticide (I), (II), or any agriculturallyacceptable salt thereof, and the numerical range is 0<X≦20; Y is theparts by weight of the flonicamid-based selective homopteran feedingblocker, and the numerical range is 0<Y≦20.
 10. The composition of claim9, wherein the ranges of weight ratios of the pesticide (I), (II), orany agriculturally acceptable salt thereof and the flonicamid-basedselective homopteran feeding blocker are X₁:Y₁ to X₂:Y₂, wherein one ofthe following conditions is satisfied: (a) X₁>Y₁ and X₂<Y₂; or (b) X₁>Y₁and X₂>Y₂; or (c) X₁<Y₁ and X₂<Y₂.
 11. A method of controlling pestscomprising applying the pesticidal composition of claim 1, near apopulation of pests, in an amount sufficient to control the pests. 12.The method of claim 11, wherein the flonicamid-based selectivehomopteran feeding blocker compound comprises flonicamid.
 13. The methodof claim 11, wherein the pests comprise sap feeding insects, chewinginsects, or both.
 14. The method of claim 11, wherein the pests comprisediamondback moth, Plutella xylostella.
 15. A method for protecting aplant from infestation and attack by pests, the method comprisingcontacting the plant with the pesticidal composition of claim 1.